Active substance combinations having insecticidal and acaricdal properties

ABSTRACT

The invention relates to insecticidal mixtures for protecting plants against attack by pests comprising
         (a) compounds of the formula (I)       

     
       
         
         
             
             
         
       
         
         
           
              in which W, X, Y, Z, A, B, D and G are each as defined in the disclosure, and 
             (b) specified agonists or antagonists of nicotinic acetylcholine receptors.3340

This application is a division of U.S. application Ser. No. 10/276,579,filed Nov. 14, 2002, now U.S. Pat. No. 6.864,276, which was filed under35 U.S.C. 371 as a national stage application of InternationalApplication No. PCT/EP01105139, filed May 7,2001, which was published inGerman as International Patent Publication WO 01/89300 on Nov. 29, 2001,which is entitled to the right of priority of German Patent ApplicationNo. 100 24 934.5, filed May 19, 2000.

The present invention relates to novel active compound combinationscomprising known cyclic ketoenols on the one hand and other knowninsecticidally active compounds on the other hand, which combinationsare highly suitable for controlling animal pests such as insects andundesired acarides.

It is already known that certain cyclic ketoenols have herbicidal,insecticidal and acaricidal properties. The activity of these substancesis good; however, at low application rates it is sometimesunsatisfactory.

Unsubstituted bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives(EP-A-355 599 and EP-A-415 211) and substituted monocyclic3-aryl-pyrrolidine-2,4dione derivatives (EP-A-377 893 and EP-A442 077)with herbicidal, insecticidal or acalicidal action are known.

Also known are polycyclic 3-arylpyrrolidine-2,4-dione derivatives(EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives (EP-A-456 063,EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885, WO 94/01 997, WO95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96/35 664, WO97/01 535, WO 97/02 243, WO 97/36 868, WO 97/43 275, WO 98/05 638, WO98/06 721, WO 98/25 928, WO 99/16 748, WO 99/24 437, WO 99/43 649, WO99/48 869 and WO 99/55 673).

Furthermore, it is already known that numerous heterocycles, organotincompounds, benzoylureas and pyrethroids have insecticidal and acaricidalproperties (cf. WO 93/22 297, WO 93/10083, DE-A-2 641 343, EP-A-347 488,EP-A-210 487, U.S. Pat. No. 3,364,177 and EP-A-234 045). However, theactivity of these substances is not always satisfactory.

It has now been found that mixtures of compounds of the formula (I)

in which

-   X represents halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy    or cyano,-   W, Y and Z independently of one another each represent hydrogen,    halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy or cyano,-   A represents hydrogen, in each case optionally halogen-substituted    alkyl, alkoxyalkyl, saturated, optionally substituted cycloalkyl, in    which optionally at least one ring atom is replaced by a heteroatom,-   B represents hydrogen or alkyl,-   A and B together with the carbon atom to which they are attached    represent a saturated or unsaturated unsubstituted or substituted    cycle which optionally contains at least one heteroatom,-   D represents hydrogen or an optionally substituted radical selected    from the group consisting of alkyl, alkenyl, alkoxyalkyl, saturated    cycloalkyl in which optionally one or more ring members are replaced    by heteroatoms,-   A and D together with the atoms to which they are attached represent    a saturated or unsaturated cycle which is unsubstituted or    substituted in the A,D moiety and optionally contains at least one    heteroatom,-   G represents hydrogen (a) or represents one of the groups

-    in which    -   E represents a metal ion or an ammonium ion,    -   L represents oxygen or sulphur,    -   M represents oxygen or sulphur,    -   R¹ represents in each case optionally halogen-substituted alkyl,        alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or        optionally halogen-, alkyl- or alkoxy-substituted cycloalkyl        which may be interrupted by at least one heteroatom, in each        case optionally substituted phenyl, phenylalkyl, hetaryl,        phenoxyalkyl or hetaryloxyalkyl,    -   R² represents in each case optionally halogen-substituted alky,        alkenyl, alkoxyalkyl, polyalkoxyalkyl or represents in each case        optionally substituted cycloalkyl, phenyl or benzyl,    -   R³ represents optionally halogen-substituted alkyl or optionally        substituted phenyl,    -   R⁴ and R⁵ independently of one another each represent in each        case optionally halogen-substituted alkyl, alkoxy, alkylamino,        dialkylamino, alkylthio, alkenylthio, cycloalkylthio or        represent in each case optionally substituted phenyl, benzyl,        phenoxy or phenylthio and    -   R⁶ and R⁷ independently of one another each represent hydrogen,        in each case optionally halogen-substituted alkyl, cycloalkyl,        alkenyl, alkoxy, alkoxyalkyl, represent optionally substituted        phenyl, represent optionally substituted benzyl or together with        the N atom to which they are attached represent an optionally        substituted ring which is optionally interrupted by oxygen or        sulphur        and at least one agonist or antagonist of acetylcholine        receptors of the formula (HI) are synergistically active and are        suitable for controlling animal pests.

Depending inter alia on the nature of the substituents, the compounds ofthe formula (I) can be present as geometrical and/or optical isomers orisomer mixtures of varying composition, which, if appropriate, can beseparated in a customary manner. The present invention provides both thepure isomers and the isomer mixtures, their preparation and use, andcompositions comprising them. Hereinbelow, for the sake of simplicity,only compounds of the formula (I) are referred to, although this meansboth the pure compounds and, if appropriate, mixtures with varyingproportions of isomeric compounds.

The agonists and antagonists of the nicotinic acetylcholine receptorsare known compounds which are known from the following publications:

-   European Published Specifications Nos. 464 830, 428 941, 425 978,    386 565, 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235    725, 212 600, 192 060, 163 855, 154 178, 136 636, 136 686, 303 570,    302 833, 306 696, 189 972, 455 000, 135 956, 471 372, 302 389, 428    941, 376 279, 493 369, 580 553, 649 845, 685 477, 483 055,580 553;-   German Offenlegungsschriften Nos. 3 639 877, 3 712 307;-   Japanese Published Specifications Nos. 03 220 176, 02 207 083, 63    307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072, 05    178 833, 07 173 157, 08 291 171;-   U.S. Pat. Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686,    5,034,404, 5,532,365;-   PCT Applications Nos. WO 91/17 659, 91/4965;-   French Application No. 2 611 114;-   Brazilian Application No. 88 03 621.

The generic formulae and definitions described in these publications,and also the individual compounds described therein, are expresslyincorporated herein by reference.

Some of these compounds are summarized under the term nitromethylenes,nitroimines and related compounds.

Preferably, these compounds can be summarized under the formula (II)

in which

-   R represents hydrogen or represents optionally substituted radicals    selected from the group consisting of acyl, alkyl, aryl, aralkyl,    heterocyclyl, heteroaryl and heteroarylalkyl;-   A′ represents a monofunctional group selected from the group    consisting of hydrogen, acyl, alkyl, aryl or represents a    bifunctional group which is linked to the radical Z′;-   E′ represents an electron-withdrawing radical;-   X′ represents the radicals —CH═ or ═N—, where the radical —CH═ may    be linked to the radical Z′ instead of an H atom;-   Z′ represents a monofunctional group selected from the group    consisting of alkyl, —O—R, —S—R,

-   -   where the radicals R are identical or different and are as        defined above,    -   or represents a bifunctional group which is linked to the        radical A′ or to the radical X′.

Particular preference is given to compounds of the formula (II) in whichthe radicals have the following meaning:

-   R represents hydrogen and represents optionally substituted radicals    selected from the group consisting of acyl, alkyl, aryl, aralkyl,    heterocyclylalkyl, heteroaryl, heteroarylalkyl.    -   Examples of acyl radicals are formyl, alkylcarbonyl,        arylcarbonyl, alkylsulphonyl, arylsulphonyl,        (alkyl-)-(aryl-)-phosphoryl, which may themselves be        substituted.    -   Examples of alkyl are C₁–C₁₀-alkyl, in particular C₁–C₄-alkyl,        specifically methyl, ethyl, i-propyl, sec- or t-butyl, which may        themselves be substituted.    -   Examples of aryl are phenyl, naphthyl, in particular phenyl.    -   Examples of aralkyl are phenylmethyl, phenethyl.    -   An example of heterocyclylalkyl is the radical

-   -   Examples of heteroaryl are heteroaryl having up to 10 ring atoms        and N, O, S, in particular N, as heteroatoms. Specific examples        are thienyl, furyl, thiazolyl, imidazolyl, pyridyl,        benzothiazolyl, pyridazinyl.    -   Examples of heteroarylalkyl are heteroarylmethyl,        heteroarylethyl having up to 6 ring atoms and N, O, S, in        particular N, as heteroatoms, in particular optionally        substituted heteroaryl as defined under heteroaryl.    -   Substituents which may be mentioned by way of example and by way        of preference are:    -   alkyl having preferably 1 to 4, in particular 1 or 2, carbon        atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and        t-butyl; alkoxy having preferably 1 to 4, in particular 1 or 2,        carbon atoms, such as methoxy, ethoxy, n- and i-propyloxy and        n-, i- and t-butyloxy; alkylthio having preferably 1 to 4, in        particular 1 or 2, carbon atoms, such as methylthio, ethylthio,        n- and i-propylthio and n-, i- and t-butylthio; halogenoalkyl        having preferably 1 to 4, in particular 1 or 2, carbon atoms and        preferably 1 to 5, in particular 1 to 3, halogen atoms, the        halogen atoms being identical or different, and preferred        halogen atoms being fluorine, chlorine or bromine, in particular        fluorine, such as trifluoromethyl, hydroxyl; halogen, preferably        fluorine, chlorine, bromine and iodine, in particular fluorine,        chlorine and bromine, cyano; nitro; amino; monoalkyl- and        dialkylamino having preferably 1 to 4, in particular 1 or 2,        carbon atoms per alkyl group, such as methylamino,        methylethylamino, n- and i-propylamino and methyl-n-butylamino;        carboxyl; carbalkoxy having preferably 2 to 4, in particular 2        or 3, carbon atoms, such as carbomethoxy and carboethoxy; sulpho        (—SO₃H); alkylsulphonyl having preferably 1 to 4, in particular        1 or 2, carbon atoms, such as methylsulphonyl and        ethylsulphonyl; arylsulphonyl having preferably 6 or 10 aryl        carbon atoms, such as phenylsulphonyl, and also heteroarylamino        and heteroarylalkylamino such as chloropyridylamino and        chloropyridylmethylamino.

-   A′ represents hydrogen or represents an optionally substituted    radical selected from the group consisting of acyl, alkyl, aryl,    which are preferably as defined under R, A′ furthermore represents a    bifunctional group. Examples include optionally substituted alkylene    having 1 to 4, in particular 1 or 2, C atoms, examples of    substituents being the substituents which have been listed further    above (and where the alkylene groups may be interrupted by    heteroatoms from the group consisting of N, O, S).

-   A′ and Z′ together with the atoms to which they are attached may    form a saturated or unsaturated heterocyclic ring. The heterocyclic    ring may contain a further 1 or 2 identical or different heteroatoms    and/or hetero groups. Preferred heteroatoms are oxygen, sulphur or    nitrogen, and preferred hetero groups are N-alkyl, where the alkyl    of the N-alkyl group contains preferably 1 to 4, in particular 1 or    2, carbon atoms. Examples of alkyl include methyl, ethyl, n- and    i-propyl, and n-, i- and t-butyl. The heterocyclic ring contains 5    to 7, preferably 5 or 6, ring members.

Examples of compounds of the formula (II) in which A′ and Z′ togetherwith the atoms to which they are attached form a ring include thefollowing:

in which

-   E′, R and X′ are each as defined above and further below.-   E′ represents an electron-withdrawing radical, specific examples    being NO₂, CN, halogenoalkylcarbonyl, such as    halogeno-C₁–C₄-alkylcarbonyl, for example COCF₃, alkylsulphonyl (for    example SO₂—CH₃), halogenoalkylsulphonyl (for example SO₂CF₃) and    with particular preference NO₂ or CN.-   X′ represents —CH═ or —N═.-   Z′ represents an optionally substituted radical selected from the    group consisting of alkyl, —OR, —SR, —NRR, where R and the    substituents are preferably as defined above.-   Z′ may, in addition to the ring mentioned above, together with the    atom to which it is attached and the radical

-    instead of X′, form a saturated or unsaturated heterocyclic ring.    The heterocyclic ring may contain a further 1 or 2 identical or    different heteroatoms and/or hetero groups. Preferred heteroatoms    are oxygen, sulphur or nitrogen and preferred hetero groups are    N-alkyl, where the alkyl or N-alkyl group contains preferably 1 to    4, preferably 1 or 2, carbon atoms. Examples of alkyl include    methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. The    heterocyclic ring contains 5 to 7, preferably 5 or 6, ring members.    Examples of the heterocyclic ring include pyrrolidine, piperidine,    piperazine, hexamethylenimine, morpholine and N-methylpiperazine.

The agonists and antagonists of the nicotinic acetylcholine receptorsare particularly preferably compounds of the formula (II) in which

-   R represents

-    where    -   n represents 0, 1 or 2, and preferably represents 1,-   Subst. represents one of the substituents mentioned above,    especially halogen, in particular chlorine, and A′, Z′, X′ and E′    are each as defined above.-   R represents in particular

The following compounds are specific examples:

Very particularly preferred agonists and antagonists of the nicotinicacetylcholine receptors are compounds of the following formulae:

in particular a compound of the following formula

Very particular preference is given to the compounds of the formulae(IIa) and (IIk).

Furthermore, very particular preference is given to the compounds of theformulae (IIe), (IIg), (IIh), (III), (IIc) and (IIm).

Preference is given to active compound combinations comprising compoundsof the formula (I) in which the radicals are as defined below:

-   W preferably represents hydrogen, C₁–C₄-alkyl, C₁–C₄-alkoxy,    chlorine, bromine or fluorine,-   X preferably represents C₁–C₄-alkyl, C₁–C₄-alkoxy,    C₁–C₄-halogenoalkyl, fluorine, chlorine or bromine,-   Y and Z independently of one another each preferably represent    hydrogen, C₁–C₄-alkyl, halogen, C₁–C₄-alkoxy or C₁–C₄-halogenoalkyl,-   A preferably represents hydrogen or in each case optionally    halogen-substituted C₁–C₆-alkyl or C₃–C₈-cycloalkyl,-   B preferably represents hydrogen, methyl or ethyl,-   A, B and the carbon atom to which they are attached preferably    represent saturated C₃–C₆-cycloalkyl in which optionally one ring    member is replaced by oxygen or sulphur and which is optionally    mono- or disubstituted by C₁–C₄-alkyl, trifluoromethyl or    C₁–C₄-alkoxy,-   D preferably represents hydrogen, in each case optionally fluorine-    or chlorine-substituted C₁–C₆-alkyl, C₃–C₄-alkenyl or    C₃–C₆-cycloalkyl,-   A and D together preferably represent in each case optionally    methyl-substituted C₃–C₄-alkanediyl in which optionally one    methylene group is replaced by sulphur.-   G preferably represents hydrogen (a) or represents one of the groups

-   -   E^((f)) and

-   -    in particular (a), (b), (c) or (g)    -   in which    -   E represents a metal ion or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur,

-   R¹ preferably represents in each case optionally halogen-substituted    C₁–C₁₀-alkyl, C₂–C₁₀-alkenyl, C₁–C₄-alkoxy-C₁–C₄-alkyl,    C₁–C₄-alkylthio-C ₁–C₄-alkyl or optionally fluorine-, chlorine-,    C₁–C₄-alkyl- or C₁–C₂-alkoxy-substituted C₃–C₆-cycloalkyl,    -   represents optionally fluorine-, chlorine-, bromine-, cyano-,        nitro-, C₁–C₄-alkyl-, C₁–C₄-alkoxy-, trifluoromethyl- or        trifluoromethoxy-substituted phenyl,    -   represents in each case optionally chlorine- or        methyl-substituted pyridyl or thienyl,

-   R² preferably represents in each case optionally fluorine- or    chlorine-substituted C₁–C₁₀-alkyl, C₂–C₁₀-alkenyl,    C₁–C₄-alkoxy-C₂–C₄-alkyl,    -   represents optionally methyl- or methoxy-substituted        C₅–C₆-cycloalkyl or    -   represents in each case optionally fluorine-, chlorine-,        bromine-, cyano-, nitro-, C₁–C₄-alkyl-, C₁–C₄-alkoxy-,        trifluoromethyl- or trifluoromethoxy-substituted phenyl or        benzyl,

-   R³ preferably represents optionally fluorine-substituted C₁–C₄-alkyl    or represents optionally fluorine-, chlorine-, bromine-,    C₁–C₄-alkyl-, C₁–C₄-alkoxy-, trifluoromethyl-, trifluoromethoxy-,    cyano- or nitro-substituted phenyl,

-   R⁴ preferably represents in each case optionally fluorine- or    chlorine-substituted C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₄-alkylamino,    C₁–C₄-alkylthio or represents in each case optionally fluorine-,    chlorine-, bromine-, nitro-, cyano-, C₁–C₄-alkoxy-,    trifluoromethoxy-, C₁–C₄-alkylthio-, C₁–C₄-halogenoalkylthio-,    C₁–C₄-alkyl- or trifluoromethyl-substituted phenyl, phenoxy or    phenylthio,

-   R⁵ preferably represents C₁–C₄-alkoxy or C₁–C₄-thioalkyl,    -   R⁶ preferably represents C₁–C₆-alkyl, C₃–C₆-cycloalkyl,        C₁–C₆-alkoxy, C₃–C₆-alkenyl, C₁–C₄-alkoxy-C₁–C₄-alkyl,

-   R⁷ preferably represents C₁–C₆-alkyl, C₃–C₆-alkenyl or    C₁–C₄-alkoxy-C₁–C₄-alkyl,

-   R⁶ and R⁷ together preferably represent an optionally methyl- or    ethyl-substituted C₃–C₆-alkylene radical in which optionally one    carbon atom is replaced by oxygen or sulphur,

-   W particularly preferably represents hydrogen, methyl, ethyl,    chlorine, bromine or methoxy,

-   X particularly preferably represents chlorine, bromine, methyl,    ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl,

-   Y and Z independently of one another each represent hydrogen,    fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl,    trifluoromethyl or methoxy,

-   A particularly preferably represents methyl, ethyl, propyl,    i-propyl, butyl, i-butyl, sec-butyl, tert-butyl, cyclopropyl,    cyclopentyl or cyclohexyl,

-   B particularly preferably represents hydrogen, methyl or ethyl,

-   A, B and the carbon atom to which they are attached particularly    preferably represent saturated C₆Cycloalkyl in which optionally one    ring member is replaced by oxygen and which is optionally    monosubstituted by methyl, ethyl, methoxy, ethoxy, propoxy or    butoxy,

-   D particularly preferably represents hydrogen, represents methyl,    ethyl, propyl, i-propyl, butyl, i-butyl, allyl, cyclopropyl,    cyclopentyl or cyclohexyl,

-   A and D together particularly preferably represent optionally    methyl-substituted C₃–C₄-alkanediyl,

-   G particularly preferably represents hydrogen (a) or represents one    of the groups

-    in which    -   M represents oxygen or sulphur,-   R¹ particularly preferably represents C₁–C₈-alkyl, C₂–C₄-alkenyl,    methoxymethyl, ethoxymethyl, ethylthiomethyl, cyclopropyl,    cyclopentyl or cyclohexyl,    -   represents optionally fluorine-, chlorine-, bromine-, cyano-,        nitro-, methyl-, ethyl-, methoxy-, trifluoromethyl- or        trifluoromethoxy-substituted phenyl,    -   represents in each case optionally chlorine- or        methyl-substituted pyridyl or thienyl,-   R² particularly preferably represents C₁–C₈-alkyl, C₂–C₄-alkenyl,    methoxyethyl, ethoxyethyl or represents phenyl or benzyl,-   R⁶ and R⁷ independently of one another each particularly preferably    represent methyl or ethyl or together represent a C₅-alkylene    radical in which the C₃-methylene group is replaced by oxygen.-   W very particularly preferably represents hydrogen or methyl,-   X very particularly preferably represents chlorine, bromine or    methyl,-   Y and Z independently of one another each very particularly    preferably represent hydrogen, chlorine, bromine or methyl,-   A, B and the carbon atom to which they are attached very    particularly preferably represent saturated C₆-cycloalkyl in which    optionally one ring member is replaced by oxygen and which is    optionally monosubstituted by methyl, methoxy, ethoxy, propoxy or    butoxy,-   D very particularly preferably represents hydrogen,-   G very particularly preferably represents hydrogen (a) or represents    one of the groups

-    in which-   M represents oxygen or sulphur,-   R¹ very particularly preferably represents C₁–C₈-alkyl,    C₂–C₄-alkenyl, methoxymethyl, ethoxymethyl, ethylmethylthio,    cyclopropyl, cyclopentyl, cyclohexyl or    -   represents optionally fluorine-, chlorine-, bromine-, methyl-,        methoxy-, trifluoromethyl-, trifluoromethoxy-, cyano- or        nitro-substituted phenyl,    -   represents in each case optionally chlorine- or        methyl-substituted pyridyl or thienyl,-   R² very particularly preferably represents C₁–C₈-alkyl,    C₂–C₄-alkenyl, methoxyethyl, ethoxyethyl, phenyl or benzyl,-   R⁶ and R⁷ independently of one another each very particularly    preferably represent methyl, ethyl or together represent a    C₅-alkylene radical in which the C₃-methylene group is replaced by    oxygen.

Particular preference is given to active compound combinationscomprising the following compounds of the formula (I)

(I)

Example No. W X Y Z R G m.p. ° C. I-1 H Br 5-CH₃ H OCH₃ CO—i-C₃H₇ 122I-2 H Br 5-CH₃ H OCH₃ CO₂—C₂H₅ 140–142 I-3 H CH₃ 5-CH₃ H OCH₃ H >220  I-4 H CH₃ 5-CH₃ H OCH₃ CO₂—C₂H₅ 128 I-5 CH₃ CH₃ 3-Br H OCH₃ H >220   I-6CH₃ CH₃ 3-Cl H OCH₃ H 219 I-7 H Br 4-CH₃ 5-CH₃ OCH₃ CO—i-C₃H₇ 217 I-8 HCH₃ 4-Cl 5-CH₃ OCH₃ CO₂C₂H₅ 162 I-9 H CH₃ 4-CH₃ 5-CH₃ OCH₃

Oil I-10 CH₃ CH₃ 3-CH₃ 4-CH₃ OCH₃ H >220   I-11 H CH₃ 5-CH₃ H OC₂H₅

Oil I-12 CH₃ CH₃ 3-Br H OC₂H₅ CO—i-C₃H₇ 212–214 I-13 H CH₃ 4-CH₃ 5-CH₃OC₂H₅ CO—n-Pr 134 I-14 H CH₃ 4-CH₃ 5-CH₃ OC₂H₅ CO—i-Pr 108 I-15 H CH₃4-CH₃ 5-CH₃ OC₂H₅ CO—c-Pr 163

The active compound combinations being well tolerated by plants andnon-toxic to warm-blooded animals are suitable for controlling animalpests, in particular insects, arachnids and nematodes found inagriculture, in forests, in the protection of stored products andmaterials and in the hygiene sector. They are preferably used as cropprotection agents. They are active against normally sensitive andresistant species, and against all or individual developmental stages.The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus,Scutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp.,Schistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example. Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp.,Damalinia spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus, Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcomi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pornonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp., Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon soistitialis, Costelytra zealandica, Lissorhoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp., Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis,Ceratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Omithodoros spp.,Dernanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp., Brevipalpus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

According to the invention, it is possible to treat all plants and partsof plants. Plants are to be understood here as meaning all plants andplant populations such as desired and undesired wild plants or cropplants (including naturally occurring crop plants). Crop plants can beplants which can be obtained by conventional breeding and optimizationmethods or by biotechnological and genetic engineering methods orcombinations of these methods, including the transgenic plants andincluding the plant cultivars which can or cannot be protected by plantbreeders' certificates. Parts of plants are to be understood as meaningall above-ground and below-ground parts and organs of plants, such asshoot, leaf, flower and root, examples which may be mentioned beingleaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seedsand also roots, tubers and rhizomes. Parts of plants also includeharvested plants and vegetative and generative propagation material, forexample seedlings, tubers, rhizomes, cuttings and seeds.

The treatment according to the invention of the plants and parts ofplants with the compounds of the formula (I) alone and in particularwith the active compound combinations is carried out directly or byaction on their environment, habitat or storage area according tocustomary treatment methods, for example by dipping, spraying,evaporating, atomizing, broadcasting, brushing-on and, in the case ofpropagation material, in particular in the case of seeds, furthermore byone- or multi-layer coating.

As already mentioned above, it is possible to treat all plants and theirparts according tQ the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding methods, such as crossing or protoplast fusion, andparts thereof, are treated. In a further preferred embodiment,transgenic plants and plant cultivars obtained by genetic engineering,if appropriate in combination with conventional rmethods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions which can be used accordingto the invention, better plant growth, increased tolerance to high orlow temperatures, increased tolerance to drought or to water or soilsalt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, better quality and/or ahigher nutritional value of the harvested products, better storagestability and/or processability of the harvested products are possiblewhich exceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by geneticengineering) which are preferred and to be treated according to theinvention include all plants which, in the genetic modification,received genetic material which imparts particularly advantageous usefultraits to these plants. Examples of such properties are better plantgrowth, increased tolerance to high or low temperatures, increasedtolerance to drought or to water or soil salt content, increasedflowering performance, easier harvesting, accelerated maturation, higherharvest yields, better quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products. Further and particularly emphasized examples ofsuch properties are a better defence of the plants against animal andmicrobial pests, such as against insects, mites, phytopathogenic fungi,bacteria and/or viruses, and also increased tolerance of the plants tocertain herbicidally active compounds. Examples of transgenic plantswhich may be mentioned are the important crop plants, such as cereals(wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape andalso fruit plants (with the fruits apples, pears, citrus fruits andgrapes), and particular emphasis is given to maize, soya beans,potatoes, cotton and oilseed rape. Traits that are particularlyemphasized are the increased defence of the plants against insects bytoxins formed in the plants, in particular those formed by the geneticmaterial from Bacillus thuringiensis (for example by the genes CryIA(a),CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb andCryIF and also combinations thereof) (hereinbelow referred to as “Btplants”). Traits that are furthermore particularly emphasized are theincreased tolerance of the plants to certain herbicidally activecompounds, for example imidazolinones, sulphonylureas, glyphosate orphosphinotricin (for example the “PAT” gene). The genes which impart thedesired traits in question can also be present in combination with oneanother in the transgenic plants. Examples of “Bt plants” which may bementioned are maize varieties, cotton varieties, soya bean varieties andpotato varieties which are sold under the trade names YIELD GARD® (forexample maize, cotton, soya beans), KnockOut® (for example maize),StarLink(® (for example maize), Bollgard® (cotton), Nucotn® (cotton) andNewLeaf® (potato). Examples of herbicide-tolerant plants which may bementioned are maize varieties, cotton varieties and soya bean varietieswhich are sold under the trade names Roundup Ready® (tolerance toglyphosate, for example maize, cotton, soya bean), Liberty Link®(tolerance to phosphinotricin, for example oilseed rape), IMI®(tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, forexample maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize). Of course, these statements also apply to plant cultivars havingthese or still-to-be-developed genetic traits, which plants will bedeveloped and/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the active compound mixturesaccording to the invention. The preferred ranges stated above for themixtures also apply to the treatment of these plants. Particularemphasis is given to the treatment of plants with the mixturesspecifically mentioned in the present text.

The ratio of the compounds of the formula (I) and the compounds of theformula (II) used, and the total amount of the mixture, depends on thenature and the occurrence of the insects. For each application, optimumratios and total amounts used can in each case be determined by testseries. In general, the ratio of compounds of the formula (I) tocompounds of the formula (II) is from 1:100 to 100:1, preferably from1:25 to 25:1 and particularly preferably from 1:5 to 5:1. These areparts by weight.

The active compound combinations can be converted into the customaryformulations such as solutions, emulsions, wettable powders,suspensions, powders, dusts, pastes, soluble powders, granules,suspension-emulsion concentrates, natural and synthetic materialsimpregnated with active compound, and microencapsulations in polymericmaterials.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants, and/or foam formers.

If the extender used is water, it is also possible, for example, to useorganic solvents as cosolvents. The following are essentially suitableas liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water.

Suitable solid carriers are:

-   -   for example ammonium salts and ground natural minerals such as        kaolins, clays, talc, chalk, quartz, attapulgite,        montmorillonite or diatomaceous earth, and ground synthetic        materials such as highly-disperse silica, alumina and silicates;        suitable solid carriers for granules are: for example crushed        and fractionated natural rocks such as calcite, marble, pumice,        sepiolite and dolomite, or else synthetic granules of inorganic        and organic meals, and granules of organic material such as        sawdust, coconut shells, maize cobs and tobacco stalks; suitable        emulsifiers and/or foam formers are: for example nonionic and        anionic emulsifiers such as polyoxyethylene fatty acid esters,        polyoxyethylene fatty alcohol ethers, for example alkylaryl        polyglycol ethers, alkylsulphonates, alkyl sulphates,        arylsulphonates, or else protein hydrolysates; suitable        dispersants are: for example lignin-sulphite waste liquors and        methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic colorants suchas alizarin colorants, azo colorants and metal phthalocyanine colorants,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound combinations according to the invention can bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with other activecompounds, such as insecticides, attractants, sterilants, bactericides,acaricides, nematicides, fungicides, growth-regulating substances orherbicides. The insecticides include, for example, phosphates,carbamates, carboxylates, chlorinated hydrocarbons, phenylureas andsubstances produced by microorganisms, inter alia.

Examples of suitable mixing components are the following:

Fungicides:

aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine,azaconazole, azoxystrobin,

benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,bromuconazole, bupirimate, buthiobate,

calcium polysulphide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan,fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentinhydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide,fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fosetyl-sodi um, fthalide,fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole,furconazole-cis, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hymexazole,

imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, irumamycin, isoprothiolane, isovaledione,

kasugamycin, kresoxim-methyl, copper preparations, such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,

paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,procymidone, propamocarb, propanosine-sodium, propiconazole, propineb,pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,

quinconazole, quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,triflumizole, triforine, triticonazole,

uniconazole,

validamycin A, vinclozolin, viniconazole,

zarilamide, zineb, ziram and also

Dagger G,

OK-8705,

OK-8801,

-   α-(1,1-dimethylethyl)-β(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,-   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,-   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,-   (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,-   1-isopropyl{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,-   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone    O-(phenylmethyl)-oxime,-   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,-   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,-   1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,-   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,-   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,-   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,-   1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,-   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,-   2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,-   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,-   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,-   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,-   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,-   2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,-   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,-   2-aminobutane,-   2-bromo-2-(bromomethyl)-pentanedinitrile,-   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,-   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,-   2-phenylphenol (OPP),-   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,-   3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,-   3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,-   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,-   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,-   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,-   8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,-   8-hydroxyquinoline sulphate,-   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,-   bis-(1-methylethyl)-3-methyl-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate-   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,-   cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,-   ethyl[(4-chlorophenyl)-azo]-cyanoacetate,-   potassium hydrogen carbonate,-   methanetetrathiol sodium salt,-   methyl    1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,-   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,-   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,-   N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,-   N-(9,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,-   N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,-   N-(4cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,-   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,-   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,-   N-(6-methoxy-3-pyridinyl)-yclopropanecarboxamide,-   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,-   N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,-   N-formyl-N-hydroxy-DL-alanine-sodium salt,-   O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   O-methyl S-phenyl phenylpropylphosphoramidothioate,-   S-methyl 1,2,3-benzothiadiazole-7-carbothioate,-   spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran]-3′-one,

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillusthuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella,bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC, bromophosA, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin, cloethocarb,clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin,cyhalothrin, cyhexatin, cypermethrin, cyromazine,

deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlorvos, diflubenzuron, dimethoat, dimethylvinphos,diofenolan, disulfoton, docusat-sodium, dofenapyn,

eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole,etrimfos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb,fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin,fenpyroximate, fenvalerate, fipronil, fluazinam, fluazuron,flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron,flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox,furathiocarb,

granulosis viruses,

halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,

imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,

nuclear polyhedrosis viruses,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, metaldehyde, methamidophos, Metharhiziumanisopliae, Metharhizium flavoviride, methidathion, methiocarb,methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,milbemectin, monocrotophos,

naled, nitenpyram, nithiazine, novaluron,

omethoat, oxamyl, oxydemethon M,

Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,phenthoat, phorat, phosalone, phosmet, phosphamidon, phoxim, pirimicarb,pirimiphos A, pirimiphos M, profenofos, promecarb, propoxur, prothiofos,prothoat, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben,pyridathion, pyrimidifen, pyriproxyfen,

quinalphos,

ribavirin,

salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,

tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil,thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate,triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron,trimethacarb,

vamidothion, vaniliprole, Verticillium lecanii

YI 5302

zeta-cyperrnethrin, zolaprofos

-   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,-   (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylate,-   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,-   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]4,5-dihydro-oxazole,-   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,-   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   3-methylphenyl propylcarbamate-   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,-   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,-   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,-   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,-   Bacillus thuringiensis strain EG-2348,-   [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,-   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl    butanoate,-   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,-   dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde-   ethyl    [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate-   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine-   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,-   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,-   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,-   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,-   O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.

Mixtures with other known active compounds such as herbicides or withfertilizers and growth regulators are also possible.

When used as insecticides, the active compound combinations according tothe invention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergists. Synergists are compounds which increase theaction of the active compounds, without it being necessary for thesynergist added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and stored-product pests, the activecompound combinations are distinguished by an excellent residual actionon wood and clay as well as good stability to alkali on limedsubstrates.

The active compound combinations according to the invention are not onlyactive against plant pests, hygiene pests and stored-product pests, butalso, in the veterinary medicine sector, against animal parasites(ectoparasites) such as hard ticks, soft ticks, mange mites, harvestmites, flies (stinging and licking), parasitizing fly larvae, lice, hairlice, bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

From the order Diptera and the suborders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Qestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica, Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyonima spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

The active compound combinations according to the invention are alsosuitable for controlling arthropods which attack agricultural livestocksuch as, for example, cattle, sheep, goats, horses, pigs, donkeys,camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, honey-bees,other domestic animals such as, for example, dogs, cats, caged birds,aquarium fish and so-called experimental animals such as, for example,hamsters, guinea pigs, rats and mice. By controlling these arthropods,cases of death and reductions in productivity (for meat, milk, wool,hides, eggs, honey and the like) should be diminished, so that moreeconomical and simpler animal husbandry is possible by the use of theactive compound combinations according to the invention.

The active compound combinations according to the invention are used inthe veterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through method, suppositories, by parenteraladministration such as, for example, by injections (intramuscularly,subcutaneously, intravenously, intraperitoneally and the like),implants, by nasal administration, by dermal administration in the formof, for example, immersing or dipping, spraying, pouring-on,spotting-on, washing, dusting, and with the aid ofactive-compound-comprising moulded articles such as collars, ear tags,tail tags, limb bands, halters, marking devices and the like.

When used for cattle, poultry, domestic animals and the like, the activecompounds can be applied as formulations (for example powders,emulsions, flowables) comprising the active compounds in an amount of 1to 80% by weight, either directly or after 100- to 10,000-fold dilution,or they may be used as a chemical dip.

Moreover, it has been found that the active compound combinationsaccording to the invention show a potent insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned by way of example and withpreference, but not by way of limitation:

Beetles such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Emobius mollis,Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis,Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec., Tryptodendronspec., Apate monachus,Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec.,Dinoderus minutus.

Dermapterans such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termnites such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zooternopsis nevadensis,Coptotermes formosanus.

Bristle-tails such as Lepisma saccharina.

Industrial materials in the present context are understood as meaningnon-living materials such as, preferably, polymers, adhesives, glues,paper and board, leather, wood, timber products and paints.

The material which is to be protected from insect attack is veryparticularly preferably wood and timber products.

Wood and timber products which can be protected by the compositionaccording to the invention, or mixtures comprising it, are to beunderstood as meaning, for example:

Construction timber, wooden beams, railway sleepers, bridge components,jetties, vehicles made of wood, boxes, pallets, containers, telephonepoles, wood lagging, windows and doors made of wood, plywood, chipboard,joinery, or timber products which quite generally are used in houseconstruction or building joinery.

The active compound combinations can be used as such, in the form ofconcentrates or generally customary formulations such as powders,granules, solutions, suspensions, emulsions or pastes.

The abovementioned formulations can be prepared in a manner known perse, for example by mixing the active compounds with at least one solventor diluent, emulsifier, dispersant and/or binder or fixative, waterrepellant, if desired desiccants and UV stabilizers, and if desiredcolorants and pigments and other processing auxiliaries.

The insecticidal compositions or concentrates used for protecting woodand timber products comprise the active compound according to theinvention in a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

The amount of composition or concentrate employed depends on the speciesand the abundance of the insects and on the medium. The optimal quantityto be employed can be determined in each case by test series uponapplication. In general, however, it will suffice to employ 0.0001 to20% by weight, preferably 0.001 to 10% by weight, of the activecompound, based on the material to be protected.

A suitable solvent and/or diluent is an organochemical solvent orsolvent mixture and/or an oily or oil-type organochemical solvent orsolvent mixture of low volatility and/or a polar organochemical solventor solvent mixture and/or water and, if appropriate, an emulsifierand/or wetter.

Organochemical solvents which are preferably employed are oily oroil-type solvents with an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C. Such oily and oil-typesolvents which are insoluble in water and of low volatility and whichare used are suitable mineral oils or their aromatic fractions ormineral-oil-containing solvent mixtures, preferably white spirit,petroleum and/or alkylbenzene.

Mineral oils with a boiling range of 170 to 220° C., white spirit with aboiling range of 170 to 220° C., spindle oil with a boiling range of 250to 350° C., petroleum and aromatics with a boiling range of 160 to 280°C., oil of terpentine, and the like are advantageously used.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boilingrange of 180 to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons with a boiling range of 180 to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene are used.

The organic oily or oil-type solvents of low volatility and with anevaporation number of above 35 and a flash point of above 30° C.,preferably above 45° C., can be replaced in part by organochemicalsolvents of high or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flash point ofabove 30° C., preferably above 45° C., and that theinsecticide-fungicide mixture is soluble or emulsifiable in this solventmixture.

In a preferred embodiment, some of the organochemical solvent or solventmixture is replaced by an aliphatic polar organochemical solvent orsolvent mixture. Aliphatic organochemical solvents which containhydroxyl and/or ester and/or ether groups are preferably used, such as,for example, glycol ethers, esters or the like.

Organochemical binders used for the purposes of the present inventionare the synthetic resins and/or binding drying oils which are known perse and which can be diluted in water and/or dissolved or dispersed oremulsified in the organochemical solvents employed, in particularbinders composed of, or comprising, an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenol resin, hydrocarbon resin such as indene/coumarone resin,silicone resin, drying vegetable and/or drying oils and/or physicallydrying binders based on a natural and/or synthetic resin.

The synthetic resin employed as binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances mayalso be used as binders, in amounts of up to 10% by weight. In addition,colorants, pigments, water repellants, odour-masking agents, andinhibitors or anticorrosive agents and the like, all of which are knownper se, can be employed.

In accordance with the invention, the composition or the concentratepreferably comprises, as organochemical binders, at least one alkydresin or modified alkyd resin and/or a drying vegetable oil. Alkydresins which are preferably used in accordance with the invention arethose with an oil content of over 45% by weight, preferably 50 to 68% byweight.

Some or all of the abovementioned binder can be replaced by a fixative(mixture) or plasticizer (mixture). These additives are intended toprevent volatilization of the active compounds, and also crystallizationor precipitation. They preferably replace 0.01 to 30% of the binder(based on 100% of binder employed).

The plasticizers are from the chemical classes of the phthalic esters,such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate,phosphoric esters such as tributyl phosphate, adipic esters such asdi-(2-ethylhexyl)-adipate, stearates such as butyl stearate or amylstearate, oleates such as butyl oleate, glycerol ethers orhigher-molecular-weight glycol ethers, glycerol esters andp-toluenesulphonic esters.

Fixatives are based chemically on polyvinyl alkyl ethers such as, forexample, polyvinyl methyl ether, or ketones such as benzophenone andethylenebenzophenone.

Other suitable solvents or diluents are, in particular, water, ifappropriate as a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

Particularly effective timber protection is achieved by industrial-scaleimpregnating processes, for example the vacuum, double-vacuum orpressure processes.

The ready-to-use compositions may if appropriate also contain otherinsecticides and if appropriate one or more additional fungicides.

The active compound combinations according to the invention can at thesame time be employed for protecting objects which come into contactwith saltwater or brackish water, such as hulls, screens, nets,buildings, moorings and signalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the active compoundcombinations according to the invention have an outstanding antifoulingaction.

Using the active compound combinations according to the invention,allows the use of heavy metals such as, for example, in bis(trialkyltin)sulphides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I)oxide, triethyltin chloride, tri-n-butyl(2-phenyl-4-chlorophenoxy)tin,tributyltin oxide, molybdenum disulphide, antimony oxide, polymericbutyl titanate, phenyl-(bispyridine)-bismuth chloride, tri-n-butyltinfluoride, manganese ethylenebisthiocarbamate, zincdimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts andcopper salts of 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzincethylene-bisthiocarbamate, zinc oxide, copper(I)ethylene-bisdithiocarbamate, copper thiocyanate, copper naphthenate andtributyltin halides to be dispensed with, or the concentration of thesecompounds substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

-   algicides such as-   2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,    dichlorophen, diuron, endothal, fentin acetate, isoproturon,    methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;

fungicides such as benzo[b]thiophenecarboxylic acid cyclohexylamideS,S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propinylbutylcarbamate, tolylfluanid and azoles such as azaconazole,cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazoleand tebuconazole;

molluscicides such as fentin acetate, metaldehyde, methiocarb,niclosamide, thiodicarb and trimethacarb; or conventional antifoulingactive compounds such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one,diiodomethylparatryl sulphone,2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium, copper,sodium and zinc salts of 2-pyridinethiol 1-oxide,pyridine-triphenylborane, tetrabutyldistannoxane,2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide and2,4,6-trichlorophenylmaleiimide.

The antifouling compositions used comprise the active compound in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions comprise the customary componentssuch as, for example, those described in Ungerer, Chem. Ind. 1985, 37,730–732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge,1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds, antifouling paints comprise, inparticular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The active compound combinationsaccording to the invention may also be incorporated into self-polishingantifouling systems.

The active compound combinations according to the invention are alsosuitable for controlling animal pests, in particular insects, arachnidsand mites, which are found in enclosed spaces such as, for example,dwellings, factory halls, offices, vehicle cabins and the like. They canbe employed alone or in combination with other active compounds andauxiliaries in domestic insecticide products for controlling thesepests. They are active against sensitive and resistant species andagainst all developmental stages. These pests include:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus,Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus, Porcellioscader.

From the order of the Diplopoda, for example, Blaniulus guttulatus,Polydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina, Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp.,Reticuliterrmes spp.

From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipieins, Culex tarsalis, Drosophila spp., Fannia

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonelia, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp., Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis, Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus, Triatoma infestans.

In the sector of household insecticides, the active compounds can alsobe used in combination with other suitable active compounds such asphosphoric esters, carbamates, pyrethroids, growth regulators or activecompounds from other known classes of insecticides.

They are used as aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

When using the active compound combinations according to the invention,the application rates can be varied within a relatively wide range,depending on the type of application. In the treatment of parts ofplants, the application rates of active compounds are generally between0.1 and 10 000 g/ha, preferably between 10 and 1 000 g/ha.

The good insecticidal and acaricidal action of the active compoundcombinations according to the invention can be seen from the exampleswhich follow. While the individual active compounds show weaknesses intheir action, the combinations show an action which exceeds a simple sumof actions.

A synergistic effect in insecticides and acaricides is always presentwhen the action of the active compound combinations exceeds the total ofthe actions of the active compounds when applied individually.

The expected action for a given combination of two active compounds canbe calculated as follows, using the formula of S. R. Colby, Weeds 15(1967), 20–22:

If

-   X is the kill rate when employing active compound A at an    application rate of m g/ha or in a concentration of m ppm,-   Y is the kill rate when employing active compound B at an    application rate of n g/ha or in a concentration of n ppm and-   E is the kill rate when employing active compounds A and B at    application rates of m and n g/ha or in a concentration of m and n    ppm,-   then

$E = {X + Y - \frac{X \cdot Y}{100}}$Here, the kill rate is determined in %. 0% means a kill rate whichcorresponds to that of the control, whereas a kill rate of 100% meansthat no infestation is observed.

If the actual effect exceeds the calculated value, the action of thecombination is superadditive, i.e. a synergistic effect is present. Inthis case, the actually observed kill rate must exceed the valuecalculated using the above formula for the expected kill rate (E).

EXAMPLE A

Aphis Gossypii Test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentrations.

Cotton leaves (Gossypium hirsutum) which are heavily infested by thecotton aphid (Aphis gossypii) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshave been killed. The kill rates that are determined are calculatedusing Colby's formula.

In this test, for example, the following active compound combinationaccording to the present application exhibits a synergistically enhancedactivity compared to the active compounds applied individually:

TABLE A Sheet 1 Plant-damaging insects Aphis gossypii test Activecompound Kill rate in % Active compounds concentration in ppm after6^(d) Ex. I-10 1.6  0 Known Ex. II-a 1.6 25 known Ex. I-10 + Ex. II-a(1:1) 1.6 + 1.6 found* Calc.** according to the invention 95 25 *found =activity found **calc. = activity calculated using Colby's formula

TABLE A Sheet 2 Plant-damaging insects Aphis gossypii test Activecompound Kill rate in % Active compounds concentration in ppm after1^(d) Ex. I-10 8  0 known Ex. II-g 8 70 known Ex. I-10 + Ex. II-g (1:1)8 + 8 found* calc.** according to the invention 95 70 *found = activityfound **calc. = activity calculated using Colby's formula

EXAMPLE B

Myzus Test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentrations.

Cabbage leaves (Brassica oleracea) which are heavily infested by thepeach aphid (Myzus persicae) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all animals have been killed; 0% means that none of theanimals have been killed. The kill rates determined are calculated usingColby's formula.

In this test, for example, the following active compound combinationaccording to the present application exhibits a synergistically enhancedactivity compared to the active compounds applied individually:

TABLE B Sheet 1 Plant-damaging insects Myzus test Active compound Killrate in % Active compounds concentration in ppm after 6^(d) Ex. I-10 1.6 5 known Ex. II-k 1.6 10 known Ex. I-10 + Ex. II-k (1:1) 1.6 + 1.6found* Calc.** according to the invention 80 14.5 *found = activityfound **calc. = activity calculated using Colby's formula

TABLE B Sheet 2 Plant-damaging insects Myzus test Active compound Killrate in % Active compounds concentration in ppm after 6^(d) Ex. I-10 1.6 0 known Ex. II-g 1.6 10 known Ex. I-10 + Ex. II-g (1:1) 1.6 + 1.6found* Calc.** according to the invention 95 10 *found = activity found**calc. = activity calculated using Colby's formula

TABLE B Sheet 3 Plant-damaging insects Myzus test Active compound Killrate in % Active compounds concentration in ppm after 1^(d) Ex. I-10 1.6 0 known Ex. II-m 1.6 15 known Ex. I-10 + Ex. II-m (1:1) 1.6 + 1.6found* calc.** according to the invention 45 15 *found = activity found**calc. = activity calculated using Colby's formula

EXAMPLE C

Critical Concentration Test/Soil Insects—Treatment of Transgenic Plants

Test insect: Diabrotica balteata—larvae in soil

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is poured on to the soil. Here, theconcentration of active compound in the preparation is virtuallyirrelevant, only the amount by weight of active compound per volume unitof soil, which is stated in ppm (mg/l), matters. The soil is filled into0.25 l pots and these are allowed to stand at 20° C.

Immediately after preparation, 5 pre-germinated maize corns of thevariety YIELD GUARD (trade mark of Monsanto Comp., USA) are placed intoeach pot. After 2 days, the test insects are placed into the treatedsoil. After a further 7 days, the efficacy of the active compound isdetermined by counting the maize plants that have emerged (1 plant=20%efficacy).

EXAMPLE D

Heliothis Virescens Test—Treatment of Transgenic Plants

Solvent: 7 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soya bean shoots (Glycine max) of the variety Roundup Ready (trade markof Monsanto Comp. USA) are treated by being dipped into the preparationof active compound of the desired concentration and are populated withthe tobacco budworm Heliothis virescens while the leaves are stillmoist.

After the desired period of time, the kill of the insects is determined.

1. A composition comprising a synergistically effective mixture of (a) acompound of the formula (I)

 in which W represents hydrogen or methyl, X represents chlorine,bromine, or methyl, Y and Z independently of one another each representhydrogen, chlorine, bromine, or methyl, A and B together with the carbonatom to which they are attached represent saturated C₆-cycloalkyl inwhich optionally one ring member is replaced by oxygen and that isoptionally monosubstituted by methyl, methoxy, ethoxy, propoxy, orbutoxy, D represents hydrogen, G represents hydrogen (a) or representsone of the groups

 in which M represents oxygen or sulphur, R¹ represents C¹–C⁸-alkyl,C²–C⁴-alkenyl, methoxymethyl, ethoxymethyl, ethylmethylthio,cyclopropyl, cyclopentyl, or cyclohexyl, represents optionallyfluorine-, chlorine-, bromine-, methyl-, methoxy-, trifluoromethyl-,trifluoromethoxy-, cyano-, or nitro-substituted phenyl, or represents ineach case optionally chlorine- or methyl-substituted pyridyl or thienyl,R² represents C¹–C⁸-alkyl, C²–C⁴-alkenyl, methoxyethyl, ethoxyethyl,phenyl, or benzyl, R⁶and R⁷ independently of one another each representmethyl or ethyl, or R⁶ and R⁷ together with the nitrogen to which theyare attached represent

 and (b) at least one agonist or antagonist of nicotinic acetylcholinereceptors selected from the group consisting of


2. A composition according to claim 1, wherein for a compound of theformula (I),

(1) W is H, X is Br, Y is 5-CH₃, Z is H, R is OCH₃, and G is CO isCO-i-C₃H₇; (2) W is H, X is Br, Y is 5-CH₃, Z is H, R is OCH₃, and G isCO₂—C₂H₅; (3) W is H, X is CH₃, Y is 5-CH₃, Z is H, R is OCH₃, and G isH; (4) W is H, X is CH₃, Y is 5-CH³, Z is H, R is OCH³, and G isCO₂—C₂H₅; (5) W is CH₃, X is CH₃, Y is 3-Br, Z is H, R is OCH₃, and G isH; (6) W is CH₃, X is CH₃, Y is 3-Cl, Z is H, R is OCH₃, and G is H; (7)W is H, X is Br, Y is 4-CH₃, Z is 5-CH₃, R is OCH₃, and G is CO-i-C₃H₇;(8) W is H, X is CH₃, Y is 4-Cl, Z is 5-CH₃, R is OCH₃, and G isCO₂—C₂H₅; (9) W is H, X is CH₃, Y is 4-CH₃, Z is 5-CH₃, R is OCH₃, and Gis

(10) W is CH₃, X is CH₃, Y is 3-CH₃, Z is 4-CH₃, R is OCH₃, and G is H;(11) W is H, X is CH₃, Y is 5-CH₃, Z is H, R is OC₂H₅, and G is

(12) W is CH₃, X is CH₃, Y is 3-Br, Z is H, R is OC₂H₅, and G isCO-i-C₃H₇; (13) W is H, X is CH₃, Y is 4-CH₃, Z is 5-CH₃, R is OC₂H₅,and G is CO-n-Pr; (14) W is H, X is CH₃, Y is 4-CH₃, Z is 5-CH₃, R isOC₂H₅, and G is CO-i-Pr; or (15) W is H, X is CH₃, Y is 4-CH₃, Z is5-CH₃, R is OC₂H₅, and G is CO-cyclopropyl.
 3. A composition accordingto claim 2 comprising a mixture of (a) the compound of formula (I) inwhich W is H, X is CH₃, Y is 5-CH₃, Z is H, R is OCH₃, and G isCO₂—C₂H₅, and (b) at least one agonist or antagonist of nicotinicacetylcholine receptors selected from the group consisting of


4. A composition according to claim 1 comprising a compound of theformula (I) and the agonist or antagonist of nicotinic acetylcholinereceptors of component (b) in a parts-by-weight ratio of from 1:100 to100:1.
 5. A method of controlling insects, arachnids, or nematodescomprising exposing insects, arachnids, or nematodes to asynergistically effective mixture comprising the composition accordingto claim
 1. 6. A process for preparing pesticides comprising mixing asynergistically effective mixture comprising the composition accordingto claim 1 with extenders and/or surfactants.